WO2020122650A1 - Électrolyte pour batterie secondaire au lithium et batterie secondaire au lithium le comprenant - Google Patents

Électrolyte pour batterie secondaire au lithium et batterie secondaire au lithium le comprenant Download PDF

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Publication number
WO2020122650A1
WO2020122650A1 PCT/KR2019/017622 KR2019017622W WO2020122650A1 WO 2020122650 A1 WO2020122650 A1 WO 2020122650A1 KR 2019017622 W KR2019017622 W KR 2019017622W WO 2020122650 A1 WO2020122650 A1 WO 2020122650A1
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Prior art keywords
secondary battery
lithium secondary
electrolyte
formula
lithium
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PCT/KR2019/017622
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English (en)
Korean (ko)
Inventor
김광연
오정우
이철행
김형태
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주식회사 엘지화학
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Priority claimed from KR1020190164881A external-priority patent/KR102473691B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US17/311,831 priority Critical patent/US20220021030A1/en
Priority to PL19895475.2T priority patent/PL3879616T3/pl
Priority to JP2021533646A priority patent/JP7118479B2/ja
Priority to EP19895475.2A priority patent/EP3879616B1/fr
Priority to CN201980081352.5A priority patent/CN113614975B/zh
Publication of WO2020122650A1 publication Critical patent/WO2020122650A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/24—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a ring other than a six-membered aromatic ring
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to an electrolyte for a lithium secondary battery and a lithium secondary battery comprising the same, and more particularly, to an electrolyte for a lithium secondary battery with improved high temperature performance and rapid charging performance and a lithium secondary battery comprising the same.
  • Lithium secondary batteries are not only portable power sources such as mobile phones, notebook computers, digital cameras and camcorders, but also power tools, electric bicycles, hybrid electric vehicles (HEVs), and plug-in hybrid electric vehicles (plug-in). HEV, PHEV), etc., its application is rapidly expanding.
  • the external shape and size of the battery are also variously changed according to the expansion of the application field and the increase in demand. In order to meet these demands, the battery components must stably implement the performance of the battery under conditions of high current.
  • the lithium secondary battery is manufactured by using a material capable of intercalating and deintercalating lithium ions as a negative electrode and a positive electrode, optionally including a separator between two electrodes, and placing an electrolyte between both electrodes, and lithium at the negative and positive electrodes Electricity is generated or consumed by a redox reaction according to insertion and desorption of ions.
  • the present invention is to solve the above problems, and to provide a lithium secondary battery electrolyte and an lithium secondary battery electrolyte having the high temperature performance of the lithium secondary battery, while improving the rapid charging performance.
  • the present invention is a lithium salt having a molar concentration of 1.5 M to 2.0M; Oligomer comprising a unit represented by the formula (1), and containing an acrylate group at the end; A first additive represented by the following Chemical Formula 2; And an organic solvent; provides an electrolyte for a lithium secondary battery comprising a.
  • Ra, Rb, Rc and Rd are each independently a fluorine element or an alkyl group having 1 to 3 carbon atoms unsubstituted or substituted with a fluorine element, and p is an integer of 1 to 50.
  • R 1 to R 4 are each independently selected from the group consisting of hydrogen and a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms.
  • the present invention provides a lithium secondary battery comprising the electrolyte for a lithium secondary battery of the present invention.
  • the electrolyte for a lithium secondary battery according to the present invention is excellent in high temperature performance, but also contains specific oligomers and additives, so that the rapid charging performance of the battery can also be improved.
  • the weight average molecular weight may mean a conversion value for standard polystyrene measured by Gel Permeation Chromatography (GPC), and unless otherwise specified, molecular weight means weight average molecular weight Can be.
  • GPC Gel Permeation Chromatography
  • a GPC condition is measured using Agilent's 1200 series, and the column used may be a Agilent's PL mixed B column, and THF may be used as a solvent.
  • the present invention is a lithium salt having a molar concentration of 1.5 M to 2.0M; Oligomer comprising a unit represented by the formula (1), and containing an acrylate group at the end; A first additive represented by the following Chemical Formula 2; And an organic solvent; provides an electrolyte for a lithium secondary battery comprising a.
  • Ra, Rb, Rc and Rd are each independently a fluorine element or an alkyl group having 1 to 3 carbon atoms unsubstituted or substituted with a fluorine element, and p is an integer of 1 to 50.
  • R 1 to R 4 are each independently selected from the group consisting of hydrogen and a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms.
  • the lithium salt may be included in the lithium secondary battery electrolyte in a molar concentration of 1.5 M to 2.0M, preferably 1.5 M to 1.9 M, more preferably 1.5 M to 1.8 M.
  • lithium ions are sufficiently supplied to improve the lithium ion yield (Li+ transference number) and the dissociation degree of lithium ions, thereby improving the output characteristics of the battery.
  • the lithium salt as an anion a compound capable of providing a lithium ion can be used without particular limitation, and specifically including Li + as the cation, used in the lithium secondary battery F -, Cl -, Br -, I -, NO 3 -, N (CN) 2 -, BF 4 -, ClO 4 -, AlO 4 -, AlCl 4 -, PF 6 -, SbF 6 -, AsF 6 -, BF 2 C 2 O 4 -, BC 4 O 8 -, (CF 3) 2 PF 4 -, (CF 3) 3 PF 3 -, (CF 3) 4 PF 2 -, (CF 3) 5 PF -, (CF 3) 6 P -, CF 3 SO 3 -, C 4 F 9 SO 3 -, CF 3 CF 2 SO 3 -, (CF 3 SO 2) 2 N -, (FSO 2) 2 N -, CF 3 CF 2 (CF 3) 2 CO -, (CF 3 SO 2) 2 CH
  • the lithium salt may include LiPF 6 and lithium imide salt.
  • Li(CF 3 SO 2 ) 2 N, Li(FSO 2 ) 2 N and Li(CF 3 CF 2 SO 2 ) 2 N may be one or more selected from the group consisting of.
  • the lithium salt includes LiPF 6 and lithium imide salt
  • the LiPF 6 and lithium imide salt are 1:1 to 1:5, preferably 1:1 to 1:4, and more preferably 1: 1 to 1:3 molar ratio.
  • the two salts are mixed and used in the molar ratio, corrosion in the battery by the electrolyte is minimized, and output characteristics of the battery can be improved.
  • the electrolyte for a lithium secondary battery of the present invention includes a unit represented by Formula 1 below, and an oligomer containing an acrylate at the terminal.
  • the Ra, Rb, Rc and Rd are each independently a fluorine element or an alkyl group having 1 to 3 carbon atoms unsubstituted or substituted with a fluorine element, and p is an integer of 1 to 50.
  • the oligomer containing the unit represented by Formula 1 and containing an acrylate group at the terminal contains an ethylene group substituted with a fluorine element having low reactivity with lithium ions, a side reaction of lithium ions and a lithium salt (salt) The decomposition reaction and the like can be controlled, and side reactions that occur when a high concentration of lithium salt is used can be suppressed.
  • the oligomer contains a fluorine element having excellent flame retardancy, when an electrolyte containing the oligomer is used, heat generation and ignition of the lithium secondary battery can be suppressed, thereby improving high-temperature safety.
  • the oligomer includes a unit containing a hydrophobic fluorine element, and at the same time, since the terminal contains a hydrophilic acrylate group, it acts as a surfactant to lower the surface resistance with the electrode interface, and the lithium secondary battery.
  • the wetting effect of can be improved.
  • the oligomer may be an oligomer represented by Formula 1A below.
  • the Ra, Rb, Rc and Rd are each independently a fluorine element or an alkyl group having 1 to 3 carbon atoms unsubstituted or substituted with a fluorine element
  • the Re is an aliphatic hydrocarbon group or an aromatic hydrocarbon group
  • the Rf is substituted with a fluorine element or Unsubstituted alkylene group having 1 to 5 carbon atoms
  • R' is hydrogen or alkyl group having 1 to 3 carbon atoms
  • o is an integer of 1 to 3
  • p is an integer of 1 to 50
  • q is 1 It is an integer of 15.
  • the p may be preferably an integer of 1 to 45, more preferably an integer of 1 to 40.
  • the aliphatic hydrocarbon group includes an alicyclic hydrocarbon group or a linear hydrocarbon group.
  • the alicyclic hydrocarbon group is a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms; A substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms containing an isocyanate group (NCO); A substituted or unsubstituted cycloalkenylene group having 4 to 20 carbon atoms; And it may include at least one selected from the group consisting of a substituted or unsubstituted heterocycloalkylene group having 2 to 20 carbon atoms.
  • the linear hydrocarbon group is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms; A substituted or unsubstituted alkylene group having 1 to 20 carbon atoms containing an isocyanate group (NCO); A substituted or unsubstituted alkoxyl group having 1 to 20 carbon atoms; A substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms; And substituted or unsubstituted alkynylene groups having 2 to 20 carbon atoms.
  • NCO isocyanate group
  • the aromatic hydrocarbon group is a substituted or unsubstituted arylene group having 6 to 20 carbon atoms; Or it may include a substituted or unsubstituted heteroarylene group having 2 to 20 carbon atoms.
  • the oligomer represented by Formula 1A may be an oligomer represented by Formula 1A-1.
  • p is an integer from 1 to 50, and q is an integer from 1 to 15.
  • the p is preferably an integer from 1 to 45, more preferably an integer from 1 to 40.
  • the oligomer may be an oligomer represented by the following Chemical Formula 1B.
  • Ra, Rb, Rc, and Rd are each independently a fluorine element or an alkyl group having 1 to 3 carbon atoms unsubstituted or substituted with a fluorine element
  • Re is an aliphatic hydrocarbon group or an aromatic hydrocarbon group
  • the Rf Is an alkylene group having 1 to 5 carbon atoms unsubstituted or substituted with a fluorine element
  • o' is an integer from 1 to 2
  • o" is an integer from 1 to 3
  • p is an integer from 1 to 50
  • the q is an integer from 1 to 15.
  • the p is preferably an integer from 1 to 45, more preferably an integer from 1 to 40.
  • the oligomer represented by Formula 1B may be an oligomer represented by Formula 1B-1.
  • p is an integer from 1 to 50, and q is an integer from 1 to 15. At this time, the p is preferably an integer from 1 to 45, more preferably an integer from 1 to 40.
  • the weight average molecular weight (MW) of the oligomer may be controlled by the number of repeating units, and may be about 500 to 200,000, specifically 1,000 to 150,000, and more specifically 2,000 to 100,000.
  • the weight average molecular weight of the oligomer is within the above range, the affinity with the organic solvent is high and dispersion can be performed well, and the surface tension can be lowered to a certain level or less to improve the wettability of the electrolyte and suppress the decomposition reaction of the lithium salt. This can prevent the lithium ions from causing side reactions.
  • the oligomer may be included in 0.1 parts by weight to 1 part by weight, preferably 0.1 parts by weight to 0.9 parts by weight, and more preferably 0.1 parts by weight to 0.8 parts by weight based on 100 parts by weight of the lithium secondary electrolyte.
  • the oligomer is included within the above range, the mobility and ionic conductivity of lithium ions are maintained at a certain level or more to act as a surfactant while suppressing side reactions, thereby minimizing the interfacial resistance in the battery.
  • R 1 to R 4 are each independently selected from the group consisting of hydrogen and a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms.
  • the first additive may be represented by the following Chemical Formula 2A.
  • the first additive may be included in an amount of 0.1 parts by weight to 1 part by weight, preferably 0.1 parts by weight to 0.8 parts by weight, and more preferably 0.1 parts by weight to 0.6 parts by weight based on 100 parts by weight of the lithium secondary electrolyte.
  • the first additive is included within the above range, it is possible to stably form an SEI film on the negative electrode surface while minimizing an increase in resistance, and prevent metal ions eluted from the positive electrode active material from adhering to the negative electrode.
  • the organic solvent can be used without limitation those commonly used in lithium secondary battery electrolyte.
  • a cyclic carbonate compound, a linear carbonate compound, an ether compound, an ester compound or an amide compound, etc. can be used alone or in combination of two or more.
  • cyclic carbonate compound examples include ethylene carbonate (EC), propylene carbonate (PC), 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, There are any one or a mixture of two or more selected from the group consisting of 2,3-pentylene carbonate, vinylene carbonate and fluoroethylene carbonate (FEC).
  • EC ethylene carbonate
  • PC propylene carbonate
  • 1,2-butylene carbonate 2,3-butylene carbonate
  • 1,2-pentylene carbonate There are any one or a mixture of two or more selected from the group consisting of 2,3-pentylene carbonate, vinylene carbonate and fluoroethylene carbonate (FEC).
  • dimethyl carbonate DMC
  • EMC ethyl methyl carbonate
  • methyl propyl carbonate methyl propyl carbonate
  • ethyl propyl carbonate methyl propyl carbonate
  • ethyl propyl carbonate methyl propyl carbonate
  • ethyl propyl carbonate methyl propyl carbonate
  • ethyl propyl carbonate methyl propyl carbonate
  • ethyl propyl carbonate ethyl propyl carbonate
  • the molecular size is small and has low viscosity properties compared to other linear carbonate compounds. , It may improve the ionic conductivity of the electrolyte more than when using other linear carbonate compounds.
  • cyclic carbonates such as ethylene carbonate, which are known to dissociate lithium salts in the electrolyte well due to high dielectric constant as a high-viscosity organic solvent among the carbonate-based organic solvents, may be used in addition to such cyclic carbonates and low viscosity such as dimethyl carbonate.
  • dielectric constant linear carbonate is mixed and used in an appropriate ratio, an electrolyte having high electrical conductivity can be prepared.
  • any one selected from the group consisting of dimethyl ether, diethyl ether, dipropyl ether, methylethyl ether, methylpropyl ether, and ethylpropyl ether, or a mixture of two or more of them may be used. It is not limited.
  • ester compound examples include linear esters such as methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, and butyl propionate; And cyclic esters such as ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -valerolactone, and ⁇ -caprolactone, or a mixture of two or more thereof. However, it is not limited thereto.
  • the electrolyte for a lithium secondary battery according to the present invention may further include a second additive.
  • a second additive it is selected from the group consisting of vinylene carbonate (VC), 1,3-propanesultone (PS), ethylene sulfate (Esa), fluorinated benzene (FB) and LiBF 4
  • VC vinylene carbonate
  • PS 1,3-propanesultone
  • Esa ethylene sulfate
  • FB fluorinated benzene
  • LiBF 4 LiBF 4
  • the second additive may be included in 1 part by weight to 15 parts by weight, preferably 1 part by weight to 12 parts by weight, more preferably 1 part by weight to 11 parts by weight with respect to 100 parts by weight of the electrolyte for the lithium secondary battery .
  • the second additive is included within the above range, while forming a film stably on the electrode and suppressing the ignition phenomenon during overcharging, a side reaction occurs during the initial activation process of the secondary battery, or additives remain or precipitate. Can be prevented.
  • a lithium secondary battery according to an embodiment of the present invention includes at least one positive electrode, at least one negative electrode, a separator that can be selectively placed between the positive electrode and the negative electrode, and the electrolyte for the lithium secondary battery. At this time, since the electrolyte for the lithium secondary battery is the same as the above, detailed description is omitted.
  • the positive electrode may be prepared by coating a positive electrode active material slurry containing a positive electrode active material, a binder for an electrode, an electrode conductive material, and a solvent on a positive electrode current collector.
  • the positive electrode current collector is not particularly limited as long as it has conductivity without causing a chemical change in the battery, for example, stainless steel, aluminum, nickel, titanium, calcined carbon, or carbon on the surface of aluminum or stainless steel. , Surface treatment with nickel, titanium, silver, and the like can be used. At this time, the positive electrode current collector may form fine irregularities on the surface to enhance the bonding force of the positive electrode active material, and may be used in various forms such as films, sheets, foils, nets, porous bodies, foams, and nonwoven fabrics.
  • the positive electrode active material is a compound capable of reversible intercalation and deintercalation of lithium, and specifically, may include a lithium composite metal oxide containing lithium and one or more metals such as cobalt, manganese, nickel or aluminum. have. More specifically, the lithium composite metal oxide is lithium-manganese oxide (eg, LiMnO 2 , LiMn 2 O 4, etc.), lithium-cobalt-based oxide (eg, LiCoO 2, etc.), lithium-nickel-based oxide (E.g., LiNiO 2, etc.), lithium-nickel-manganese oxide (e.g., LiNi 1-Y1 Mn Y1 O 2 (here, 0 ⁇ Y1 ⁇ 1), LiMn 2-z1 Ni z1 O 4 ( Here, 0 ⁇ Z1 ⁇ 2), etc.), lithium-nickel-cobalt oxide (for example, LiNi 1-Y2 Co Y2 O 2 (here, 0 ⁇ Y2 ⁇ 1), etc.), lithium-manganese
  • the lithium composite metal oxide is LiCoO 2 , LiMnO 2 , LiNiO 2 , lithium nickel manganese cobalt oxide (for example, Li(Ni 0.6 Mn 0.2 Co 0.2 )O 2 in that the capacity and stability of the battery can be improved.
  • the lithium composite metal oxide is Li(Ni 0.6 Mn 0.2 Co 0.2 )O 2 , considering the remarkable effect of improvement according to the type and content ratio control of the constituent elements that form the lithium composite metal oxide.
  • the electrode binder is a component that assists in bonding the positive electrode active material and the electrode conductive material and bonding to the current collector.
  • polyvinylidene fluoride polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene (PE) , Polypropylene, ethylene-propylene-diene polymer (EPDM), sulfonated EPDM, styrene-butadiene rubber, fluorine rubber, and various copolymers.
  • the electrode conductive material is a component for further improving the conductivity of the positive electrode active material.
  • the electrode conductive material is not particularly limited as long as it has conductivity without causing a chemical change in the battery.
  • graphite Carbon-based materials such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, and thermal black
  • Conductive fibers such as carbon fibers and metal fibers
  • Metal powders such as carbon fluoride, aluminum, and nickel powders
  • Conductive whiskey such as zinc oxide and potassium titanate
  • Conductive metal oxides such as titanium oxide
  • Conductive materials such as polyphenylene derivatives may be used.
  • conductive materials include acetylene black-based Chevron Chemical Company, Denka Singapore Private Limited, Gulf Oil Company, etc., Ketjenblack, EC Series (manufactured by Armak Company), Vulcan XC-72 (manufactured by Cabot Company) and Super P (manufactured by Timcal).
  • the solvent may include an organic solvent such as NMP (N-methyl-2-pyrrolidone), and may be used in an amount that becomes a desirable viscosity when the positive electrode active material and, optionally, a binder and a positive electrode conductive material are included. have.
  • NMP N-methyl-2-pyrrolidone
  • the negative electrode may be prepared by coating a negative electrode active material slurry containing a negative electrode active material, an electrode binder, an electrode conductive material, and a solvent on a negative electrode current collector, for example. Meanwhile, the cathode may use the metal current collector itself as an electrode.
  • the negative electrode current collector is not particularly limited as long as it has high conductivity without causing a chemical change in the battery.
  • copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper or stainless steel Surface-treated with carbon, nickel, titanium, silver, etc. on the surface, aluminum-cadmium alloy, or the like can be used.
  • it is also possible to form fine irregularities on the surface to enhance the bonding force of the negative electrode active material and may be used in various forms such as films, sheets, foils, nets, porous bodies, foams, and nonwoven fabrics.
  • the negative electrode active material examples include natural graphite, artificial graphite, and carbonaceous materials; Lithium-containing titanium composite oxides (LTO), metals (Me) which are Si, Sn, Li, Zn, Mg, Cd, Ce, Ni, or Fe; Alloys composed of the metals (Me); Oxides (MeOx) of the metals (Me); And one or two or more negative electrode active materials selected from the group consisting of a composite of the metals (Me) and carbon.
  • LTO Lithium-containing titanium composite oxides
  • metals (Me) which are Si, Sn, Li, Zn, Mg, Cd, Ce, Ni, or Fe
  • Oxides (MeOx) of the metals (Me) And one or two or more negative electrode active materials selected from the group consisting of a composite of the metals (Me) and carbon.
  • a conventional porous polymer film conventionally used as a separator such as ethylene homopolymer, propylene homopolymer, ethylene/butene copolymer, ethylene/hexene copolymer and ethylene/methacrylate copolymer, etc.
  • a porous polymer film made of a polymer may be used alone or by laminating them, or a conventional porous nonwoven fabric, such as a high melting point glass fiber, a polyethylene terephthalate fiber, or the like, may be used, but is not limited thereto. no.
  • a non-aqueous organic solvent was prepared by adding ethylene carbonate (EC):dimethyl carbonate (DMC) to an organic solvent containing a 1:9 volume ratio so that the molar concentration of LiPF 6 was 1.5M.
  • a liquid electrolyte for a lithium secondary battery was prepared.
  • a positive electrode active material in solvent N-methyl-2-pyrrolidone (NMP) (((Li(Ni 0.8 Co 0.1 Mn 0.1 )O 2 ), NCM811): conductive material (bundled carbon nanotube): binder (polyvinyl Lidenfluoride (PVDF)) was mixed in a weight ratio of 97.7:0.3:2 to prepare a positive electrode active material slurry
  • the positive electrode active material slurry was applied to a positive electrode current collector (Al thin film) having a thickness of 20 ⁇ m, dried and rolled ( A positive electrode was prepared by performing roll press.
  • a negative electrode active material slurry was prepared by mixing a negative electrode active material (graphite (AGP8)): SiO in a ratio of 95:5 in distilled water as a solvent.
  • the negative electrode active material slurry was applied to a negative electrode current collector (Cu thin film) having a thickness of 10 ⁇ m, and dried and roll pressed to prepare a negative electrode.
  • the pouch type A lithium secondary battery was manufactured by injecting the electrolyte for a lithium secondary battery into a secondary battery case.
  • a lithium secondary battery was manufactured in the same manner as in Example 1, except that the liquid electrolyte for the lithium secondary battery was injected.
  • a liquid electrolyte for a lithium secondary battery When preparing an electrolyte for a lithium secondary battery, a liquid electrolyte for a lithium secondary battery and the same method as in Example 1, except that an organic solvent containing ethylene carbonate (EC):ethyl methyl carbonate (EMC) in a 1:9 volume ratio was used. A lithium secondary battery was prepared.
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • a non-aqueous organic solvent was prepared by adding ethylene carbonate (EC):dimethyl carbonate (DMC) to an organic solvent containing a 1:9 volume ratio so that the molar concentration of LiPF 6 was 1.5M.
  • a liquid electrolyte for a lithium secondary battery was prepared by adding 3 g of vinylene carbonate (VC) as an additive.
  • a lithium secondary battery was manufactured in the same manner as in Example 1, except that the liquid electrolyte for the lithium secondary battery was injected.
  • ESa ethylene sulfate
  • FB fluorinated benzene
  • an electrolyte for a lithium secondary battery and a lithium secondary battery were prepared in the same manner as in Example 1, except that no oligomer was added.
  • an electrolyte for a lithium secondary battery and a lithium secondary battery were prepared in the same manner as in Example 1, except that the first additive was not added.
  • a lithium secondary battery electrolyte and a lithium secondary battery were prepared in the same manner as in Example 1, except that the molar concentration of LiPF 6 was added to 1.0M.
  • a lithium secondary battery electrolyte and a lithium secondary battery were prepared in the same manner as in Example 1, except that the molar concentration of LiPF 6 was added to 3.0 M.
  • an electrolyte for a lithium secondary battery and a lithium secondary battery were prepared in the same manner as in Example 1, except that both the oligomer and the first additive were not used.
  • the discharge capacity at this time was set as the initial capacity. Thereafter, 4.2 V, 660 mA (0.33 C, 0.05 C cut-off) CC/CV charging and 2.5 V, 660 mA (0.33 C) CC discharge were performed 100 times at high temperatures (45° C.), respectively. Then, the capacity retention rate was calculated by comparing the 100th discharge capacity with the initial capacity, and the results are shown in Table 1.
  • the high-temperature capacity retention rate of the lithium secondary battery manufactured according to the embodiment is higher than that of the lithium secondary battery manufactured according to the comparative example.
  • the lithium secondary batteries prepared in Examples 1 to 5 and Comparative Examples 1 to 5 were charged at a constant current/constant voltage condition up to 4.2V at a rate of 0.33C and subjected to 0.05C cut off charging, and then discharged at 0.33C 2.5V.
  • the discharge capacity of was set as the initial discharge capacity.
  • constant current/constant voltage conditions were charged to 4.2V at 0.33C rate and 0.05C cut off was charged, and the remaining capacity over time was measured while being stored at 60°C for 2 weeks.
  • Table 2 shows the high-temperature capacity retention rate (%) based on the initial discharge capacity (100%).
  • the capacity retention rate of the lithium secondary battery manufactured according to the embodiment is higher than that of the lithium secondary battery manufactured according to the comparative example.
  • Example 1 using dimethyl carbonate which is a linear carbonate having low viscosity and low dielectric constant
  • Example 3 using ethyl methyl carbonate instead of dimethyl carbonate as linear carbonate You can confirm that.
  • the C/rate is set for each SOC section from SOC 8% to SOC 80%.
  • the charge amount when charging in CV mode was recorded. And it discharged to SOC 8% again in 0.1C in CC mode. Afterwards, charging/discharging is performed once as one cycle. Subsequently, the charging capacity (%) after 50 cycles of the initial charging capacity (100%) was defined as a rapid charging capacity retention rate (%), and is shown in Table 4.
  • Example 4 the retention rate of the rapid charge capacity of Example 1 using dimethyl carbonate, which is a linear carbonate having low viscosity and low dielectric constant, is higher than Example 3 using ethyl methyl carbonate instead of dimethyl carbonate as linear carbonate. You can see that it is higher.

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Abstract

La présente invention porte sur un électrolyte pour batterie secondaire au lithium et sur une batterie secondaire au lithium le comprenant, l'électrolyte comprenant : un sel de lithium dont la concentration molaire est comprise entre 1,5 et 2,0 M ; un oligomère comprenant une unité représentée par la formule chimique (1) et contenant un groupe acrylate à une de ses extrémités ; un premier additif représenté par la formule chimique (2) ; et un solvant organique.
PCT/KR2019/017622 2018-12-13 2019-12-12 Électrolyte pour batterie secondaire au lithium et batterie secondaire au lithium le comprenant WO2020122650A1 (fr)

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US17/311,831 US20220021030A1 (en) 2018-12-13 2019-12-12 Electrolyte For Lithium Secondary Battery And Lithium Secondary Battery Including The Same
PL19895475.2T PL3879616T3 (pl) 2018-12-13 2019-12-12 Elektrolit dla akumulatora litowego i zawierający go akumulator litowy
JP2021533646A JP7118479B2 (ja) 2018-12-13 2019-12-12 リチウム二次電池用電解質及びこれを含むリチウム二次電池
EP19895475.2A EP3879616B1 (fr) 2018-12-13 2019-12-12 Électrolyte pour batterie secondaire au lithium et batterie secondaire au lithium comprenant celui-ci
CN201980081352.5A CN113614975B (zh) 2018-12-13 2019-12-12 锂二次电池用电解质和包含该电解质的锂二次电池

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US6927001B1 (en) * 1999-05-24 2005-08-09 Ube Industries, Ltd. Non-aqueous electrolytic solution and lithium secondary battery
KR101201272B1 (ko) * 2003-07-17 2012-11-14 우베 고산 가부시키가이샤 리튬 이차전지용 비수전해액 및 그것을 사용한 리튬이차전지
JP2014235986A (ja) * 2013-06-05 2014-12-15 富士フイルム株式会社 非水二次電池用電解液および非水二次電池
KR20160040127A (ko) 2014-10-02 2016-04-12 주식회사 엘지화학 젤 폴리머 전해질 및 이를 포함하는 리튬 이차전지
KR20180026358A (ko) * 2016-09-02 2018-03-12 주식회사 엘지화학 젤 폴리머 전해질 및 이를 포함하는 리튬 이차전지

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CN108886165B (zh) 2016-12-08 2021-06-04 株式会社Lg化学 用于锂二次电池的电解质和包括该电解质的锂二次电池
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JP2014235986A (ja) * 2013-06-05 2014-12-15 富士フイルム株式会社 非水二次電池用電解液および非水二次電池
KR20160040127A (ko) 2014-10-02 2016-04-12 주식회사 엘지화학 젤 폴리머 전해질 및 이를 포함하는 리튬 이차전지
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